DE69733532T2 - FILM OF HYBRID POLYMER - Google Patents

Description

TECHNICAL TERRITORY

The The present invention relates generally to thin metallized and non-metallized Polymer films, the further coatings and surface functionalization which has application specific properties such as improved Thermal stability, Abrasion resistance, Moisture barrier and confer optical properties that make these films useful in food packaging applications, Electrical applications that include film capacitors and cables, magnetic tapes with evaporated metal, printing, decorative envelopes and optically variable Films for Make security applications usable.

TECHNICAL BACKGROUND

metallized and non-metallized films are commonly used in a variety of ways used by electrical, packaging and decorative applications. Although the field of application is very broad, the desired Characteristics of the different films basically the same. These desired Properties include mechanical strength, thermal and chemical Resistance, Abrasion resistance, moisture and oxygen barrier property and surface functionality, the one Wetting, adhesion, gliding and the like. Supported. As a result, a variety of hybrid films have been developed serve a wide range of applications.

Generally use hybrid metallized and polymer coated films Variety of production processes. For example, metallized Polymer films usual way corona, flame or plasma treated to promote adhesion of the metal to the polymer surface (US patents 5,019,210 and 4,740,385); or ion beam treated and then electron beam treated, around the adhesion and leveling the film on a substrate by electrostatic To promote power (U.S. Patent 5,087,476). Polymer coatings, the various Functions such as printability, adhesion promotion, abrasion resistance, optical and electrical properties, have been used various techniques, thermosetting, reactive polymerization, Plasma polymerization (U.S. Patent 5,322,737) and radiation curing under Using ultraviolet and electron beam radiation, (U.S. Patents 5,374,483, 5,445,871, 4,557,980, 5,225,272, U.S. Pat. 5 068 145, 4 670 340, 4 720 421, 4 781 965, 4 812 351, 4 67 083 and 5,085,911). In such applications, a monomeric material using conventional techniques the roll coating, casting, spraying and the like. Applied and the coating afterwards under conditions of atmospheric Pressure polymerizes.

In younger At the time, a new technique was developed which made the radiation-curing formation process Vacuum coatings using a flash evaporation technique allows for forming a thin liquid monomer deposited from the vapor phase leads, that cured by radiation (US Pat. Nos. 4,842,893, 4,954,371 and 5,032,461 and US Pat European Patent Application 0 339 844). This technique overcomes the limitations conventional Techniques for the application of liquid Monomers and requires relatively low radiation doses for polymerization.

It was determined to be that described in the above references Vacuum polymer coating technology has some crucial limitations with regard to certain mechanical, thermal, chemical and has morphological properties that their usability in packaging films, capacitors, magnetic tapes with vapor-deposited metal and optically variable films. The invention disclosed herein overcomes these problems and extends the single-stage polymer-and-metal vacuum coating technology on new functional products with a unique set of properties.

EPIPHANY THE INVENTION

task the present invention is the production of a hybrid polymer film, the excellent mechanical, thermal, chemical and surface morphological Features. In conjunction with one or more metal coatings or a ceramic coating, the hybrid film can be used for production improved packaging films, film capacitors, magnetic tapes with evaporated metal and optically variable films are used.

task this invention is also the production of hybrid films with controlled surface micro-roughness. This includes films that have a smoother surface than the base film or a surface having controlled microroughness.

Preferably can the hybrid polymer films by an improved method of application, Polymerization and discharge of one or more layers of under vacuum deposited radiation-curable monomer films, the for the production of the hybrid polymer film in a single stage continuous Procedures used to be produced.

According to the present The invention encompasses the hybrid polymer film as defined in claim 1 a first polymer film having a plasma treated surface and a second polymer film having first and second surfaces, wherein the first surface the second polymer film is longitudinal the first plasma-treated surface of the first polymer film wherein a vacuum-deposited radiation-polymerized Monomer film is deposited on the plasma-treated surface and this Monomer film has a plasma-treated surface.

The base films or first polymer films used in the invention to produce the hybrid films are selected from a group of thermoplastic films including polypropylene, polyethylene terephthalate, high and low density polyethylene, polycarbonate, polyethylene-2,6-naphthalate, nylon, polyvinylidene difluoride, Polyphenylene oxide and polyphenylene sulfide, and thermosetting films comprising cellulose derivatives, polyimide, polyimidebenzoxazole and polybenzoxazole. The second polymer films are radiation polymerized monomer films which are multifunctional acrylate or acrylate containing monomers capable of free radical polymerization double bonds. Plasma treatment with gases from the group of N ₂ , Ar, Ne, O ₂ , CO _2, and CF ₄ is used to functionalize the base film, to further improve the crosslinking of the acrylate film surface and to remove surface charge, which improves the winding and unwinding of the hybrid film , used. Inorganic layers can be used in combination with the polymer layers to produce hybrid films of various end uses; Such inorganic layers include metals selected from the group consisting of aluminum, zinc, nickel, cobalt, iron, iron on aluminum, zinc on silver, zinc on copper and zinc on aluminum, nickel-cobalt alloys and nickel-cobalt-iron alloys and ceramics selected from the group of alumina, silicon oxides (SiO _x , where x = 1 to 2), tantalum oxide, aluminum nitride, titanium nitride, silicon nitride, silicon oxynitride, zinc oxide, indium oxide and indium tin oxide.

Of the Hybrid polymer film shows both improved corrosion resistance as well as current carrying capacity of metallized capacitors in the Comparison to polymer films of the prior art and overall reliability in demanding applications, the operations in extreme conditions of voltage / current and temperature require.

at Incorporation in food packaging improves the presence the acrylate polymer on a thermoplastic polymer, such as polypropylene, the oxygen and Moisture barrier feature metallized and ceramic coated Movies and it also improves the mechanical properties of the Barrier layer to the extent that less damage the barrier layer as a function of the film stretch takes place.

By Adjusting the chemistry of the acrylate coatings can be the surface of the Hybrid films hydrophobic / hydrophilic, oleophobic / oleophilic and to a Combination of the same. This can be an adaptation for different Printing inks for Packaging film applications in addition to improve the barrier properties. Such a, in metallized printable one-step process Film eliminates the lamination of another polymer film, the to protect the metal layer and used to provide a printable surface becomes.

hybrid films can reduced surface micro-roughness thus eliminating the need for costly flat films for magnetic tape applications is eliminated. Increased and controlled surface micro-roughness on a hybrid film can lead to less abrasion damage and the formation of unique interference effects causes color shifts if changed Viewing angle.

at Incorporation into flexible electrical cables to prevent fluorinated acrylate polymers, those on thermosetting Polymer films such as polyimide, polyimidebenzoxazole (PIBO) and polybenzoxazole (PBO) are deposited, electrical creep, and they char only in the presence of an electric arc.

at decorative and security applications usable color shifting effects can in a one-step process with low costs through appropriate Choice of thickness of the metal and polymer layers are produced.

SHORT DESCRIPTION THE DRAWINGS

1 is a schematic of an apparatus useful in carrying out the method of making the polymer film of the invention;

2 with the coordinates of electrical resistance (in ohms) and time (in hours) is a graph showing the changes in electrical resistance due to corrosion of aluminum deposited on a control polypropylene (PP) film and a PP / plasma / acrylate Hybrid film deposited with the aluminum-metallized films exposed to temperature and humidity ambient conditions of 70 ° C and 85% relative humidity, respectively;

3A -E shows various combinations of films that can be deposited on a film substrate that has an acrylate film on the substrate ( 3A ), a metal film on an acrylate film on the substrate ( 3B ), an acrylate film on a metal film on an acrylate film on the substrate ( 3C ), an acrylate film on a metal film on the substrate ( 3D ) and both sides of the substrate are coated with an acrylate film ( 3E );

4 with the coordinates of the increase in electrical resistance (in%) and elongation (in%) is a plot of the increase in electrical resistance as a function of strain, indicative of corrosion resistance, for an untreated metallized polymer film, and for a metallized polymer film is plasma treated;

5 with the coordinates of the increase in electrical resistance (in%) and elongation (in%) is a plot of the increase in electrical resistance as a function of strain for an untreated polymer film and for a metallized polymer film that is plasma treated and coated;

6 is, with the coordinates of the number of samples and the oil / water index, a plot of the degree of wetting by oil-and-water based fluids on polymer samples;

7A Fig. 3 is a sectional view of an acrylate-coated polypropylene film in which the surface of the acrylate coating is micro-roughened;

7B is a sectional view of the coated polymer film of 7A after deposition of a thin layer of metal on the micro-roughened surface of the acrylate coating and

8th Figure 4 is a sectional view of the hybrid polymer film according to the invention configured for optical filter applications.

BEST TYPE AND WAY OF IMPLEMENTATION THE INVENTION

It has been found that the vacuum polymer coating technique described in US Pat. Nos. 4,842,893, 4,954,371 and 5,032,461 and European Patent Application 0 339 844 has some significant limitations, including:
(a) When an acrylate monomer material is deposited on a polymer film substrate, oxygen adsorbed on the surface of the film absorbs radiation-induced free radicals and thereby inhibits the polymerization process at the interface; (b) contaminants and low molecular weight species on the surface of most polymeric materials can inhibit wetting of the vapor phase deposited liquid monomer, resulting in thin polymer films with poor uniformity; (c) if this process is used to make coatings on a polymeric web moving at high speed, the polymer coating does not always achieve 100% polymerization; and (d) when electron radiation is used to cure the acrylate monomers, electrons trapped on the surface of the film cause an electrostatic charge. The combination of partial cure and electrostatic charge (trapped electrons) on the film surface can cause blocking or sticking of the film to itself when wound into a roll.

The The following discussion is mainly on a hybrid film, the polypropylene (PP), which with a coated under vacuum deposited radiation-curable acrylate monomer film is that polymerized on curing is included. However, it goes without saying that this discussion is only exemplary and it is not intended to limit the composition of the coated polymer or the presence or absence mean a metal coating on the hybrid film.

Of the Hybrid film comprises a PP film coated with a high temperature crosslinked acrylate polymer, which has been deposited by a rapid vacuum method is. The basic aspects of the process are disclosed in U.S. Patents 4,842 893, 4,954,371 and 5,032,461. However, that's the procedure for the Modified for purposes of the present invention.

1 shows an example of the device 10 which is conveniently used in the practice of the present invention. A vacuum chamber 12 is with a vacuum pump 14 which evacuates the chamber to the appropriate pressure. The essential components of the device 10 in the vacuum chamber 12 include a rotating drum 16 , a source coil of the polymer film 20 , a recording reel 22 for winding up the coated polymer film 20 ' , suitable guide rollers 24 . 26 , a monomer evaporation device 28 for depositing a thin film of an acrylate monomer or mixture containing an acrylate monomer on the polymer film and radiation curing agent 30 such as an electron beam gun, for crosslinking the acrylate monomer to form a radiation cured acrylate polymer.

Optionally, an evaporation system 32 for depositing an inorganic film on the acrylate film. Further, optionally, a second monomer evaporation device 128 and radiation curing agents 130 behind the resistance evaporation system 32 be positioned. These optional aspects are discussed in more detail below.

The vacuum used in the practice of the invention is less than about 0.001 atmospheres or less than about 1 millibar. Typically, the vacuum is of the order of 2 × 10 ^-4 to 2 × 10 ^-5 Torr.

In operation, the polymer film 20 from the source coil 18 the rotating drum 16 which rotates in the direction indicated by the arrow "A", via the guide roller 24 fed. The polymer film passes through several stations, starting from the surface of the rotating roller 16 through the guide roller 26 removed and through the take-up spool 22 as a coated film 20 ' added. When the polymer film 20 from the source coil 18 is removed, he goes through a first plasma treatment unit 36 where the surface of the film to be coated is exposed to a plasma to remove adsorbed oxygen, moisture and any low molecular weight species from the surface of the film before the acrylate is formed thereon. Immediately before winding the coated polymer film 20 ' on the take-up spool 22 he goes through a second plasma treatment unit 38 where the coated surface of the film is exposed to a plasma to complete the curing of the acrylate coating and to remove any accumulated electrical charge.

The Conditions of plasma treatment are not critical, and the Plasma source can be low frequency RF, high frequency RF, DC or alternating current.

The rotating drum 16 is a water-cooled drum driven by a motor (not shown). The drum 16 is cooled to a specific temperature for the particular monomer used, and generally to the range of -20 ° C to 50 ° C, to allow condensation of the monomer (in vapor form). The drum 16 is rotated at a surface speed in the range of 1 to 1000 cm / second.

The polymer film 20 For example, any of the polymers having the properties required for the treatment described below may comprise. Examples of such polymers include the thermoplastic polymers such as polypropylene (PP), polyethylene terephthalate (PET), polycarbonate, polyethylene-2,6-naphthalate, polyvinylidene difluoride, polyphenylene oxide and polyphenylene sulfide, and the thermosetting polymers such as polyimide, polyimidebenzoxazole (PIBO), polybenzoxazole (PBO) and cellulose derivatives.

The acrylate monomer becomes on the polymer film 20 through the monomer evaporation device 28 containing liquid monomer from a container 40 by an ultrasonic atomizing device 42 where, by means of heaters (not shown), the monomer liquid is immediately evaporated, ie flash evaporated, to avoid the possibility of polymerization prior to deposition on the polymer film 20 to minimize, deposited. The specific aspects of this part of the process are described in more detail in the aforementioned U.S. Patents 4,842,893, 4,954,371 and 5,032,461 and do not form part of the present invention.

The flash evaporated monomer condenses on the surface of the polymer film 20 coming from the cooled rotating drum 16 is worn, where it forms a thin monomer film.

The condensed liquid monomer is next passed through the radiation curing agent 30 radiation-hardened. The radiation curing agent may include any of the conventional methods of opening the double bonds of the acrylate monomer; Examples of suitable means include devices that emit electron or ultraviolet radiation. Preferably, the radiation curing agent comprises 30 a thermionic or gas-discharge electron beam gun. The electron beam gun directs an electron beam at the monomer, thereby hardening the material into a polymerized crosslinked film. Hardening is accomplished by adjusting the electron beam voltage to the acrylate monomer thickness on the polymer film 20 controlled. For example, an electron voltage in the range of about 8 to 12 keV cures a thickness of about 1 μm of deposited monomer. With regard to the details regarding the deposition of the acrylate monomer, the specific aspects of this part of the process are described in the aforementioned U.S. Patents 4,842,893, 4,954,371 and 5,032,461 and do not form part of the present invention.

3A shows the coated film 20 ' at this stage, an acrylate polymer film 122 on a polymeric film web or polymer film substrate 120 includes. Such a coated film 20 ' has a variety of uses including high-temperature electric cables and film capacitors wound with a metal foil.

The cured acrylate monomer or crosslinked polymer then passes through the optional resistance evaporation system 32 where an inorganic material such as aluminum or zinc, if desired, can be deposited on the cured monomer layer. Two such coated films 20 ' can be wound to form metallized capacitors. 3B shows a coated film 20 ' with a metallized layer 124 on the acrylate polymer film 122 ,

The same material can be used for food packaging films, preferably with an additional acrylate coating over the aluminum metal layer to protect the thin metal layer and therefore to improve the barrier properties of the film. 3C and 3D show two other configurations that are useful in food packaging. In 3C is the additional acrylate coating 122 ' on top of the metal film 124 formed while in 3D the metal film first on the polymer film substrate 120 is deposited, whereupon the deposition of the acrylate film 122 follows on this. The method of forming each of these configurations is discussed in more detail below.

The resistance evaporation system 32 is commonly used in the field of metallization of films. Alternatively, other metal deposition systems such as conventional electron beam evaporation apparatus and magnetron sputtering may be used. The resistance evaporation system 32 is continuously using a metal source from the wire feed 44 provided.

The deposition of the metal film can be avoided, thereby simply forming a hybrid polymer film which can have a variety of uses as described above with reference to FIG 3A provided.

After the optional metallization step, a second optional acrylate monomer deposit can be made using the monomer evaporation device 128 and the radiation curing agent 130 be performed. This second deposit is used to form the in 3C and 3D shown coated films 20 ' used discussed above. The composition of the second acrylate film 122 ' can be compared to the first acrylate film 122 be the same or different.

In the 1 The device shown is primarily for the formation of an acrylate film 122 . 122 ' on top of another polymer film 120 with or without a metal layer 124 directed. Furthermore, the uncoated side of the polymer film could 20 also with an acrylate film 222 the same or a different composition, for example by providing a second rotating drum with the vacuum chamber 12 and providing the same series of devices (monomer evaporation device 28 and radiation curing agents 30 with optional metallization device 32 ) are coated. Such a coated film 20 ' is in 3E shown.

The acrylate polymer film 122 . 222 is formed to a thickness in the range of about 0.01 to 12 μm, depending on the particular application. Although thicker films than this can be made, no advantage seems to be derived from the use of such thicker films.

The thickness of the polymer film substrate 20 . 120 is typically in the range of about 1 to 100 μm, which again depends on the specific application.

When used with conventional polymer films used in metallized capacitors, such as PP, PET or polycarbonate, the thickness of the acrylate film is 122 . 222 typically of the order of 0.1 to 1 μm.

In such cases, the underlying base film (PP or polycarbonate) 20 . 120 much thicker, with commercially available PP films ranging from 4 to 25 microns. Metallized thin film PP capacitors are used in low loss AC applications and the presence of the acrylate film provides a number of advantages that include greater reliability and unexpectedly improved corrosion resistance. The dielectric constant of the acrylate film for use in such applications is preferably in the range of about 2.5 to 4.0.

on the other hand There are applications that require energy storage, where higher permittivity in the range of 10 to 15 desired are. In such cases become acrylate polymers with such a high dielectric constant on thinner ones Deposited films, and therefore the acrylate film comprises a substantial Fraction of the hybrid film thickness.

For packaging applications, the acrylate coatings are 122 . 222 typically 0.5 to 2.0 μm thick, based on PP or PET films 20 . 120 , which are typically 12 to 35 microns thick, deposited.

Examples for acrylate monomers, in the implementation of the present invention include ethoxylated Bisphenol diacrylate, hexadioldiacrylate, phenoxyethyl acrylate, acrylonitrile, 2,2,2-trifluoromethyl acrylate, Triethylene glycol diacrylate, isodecyl acrylate, alkoxylated diacrylate, Tripropylene glycol diacrylate, ethoxyethyl acrylate, polyethylene glycol diacrylate, Diethylene glycol diacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, Cyanoethyl (mono) acrylate, octodecyl acrylate, dinitrile acrylate, pentafluorophenyl acrylate, Nitrophenyl acrylate, isobornyl acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, Tetrahydrofurfuryl acrylate, neopentyl glycol diacrylate, propoxylated Neopentylglycol diacrylate and mixtures thereof.

The metal film 124 which is deposited in the case of metallized capacitors may comprise aluminum or zinc or a composite film of nickel on aluminum, iron on aluminum, zinc on silver, zinc on copper or zinc on aluminum. The thickness of the metal film 124 for use with capacitors is of the order of 100 to 300 Å and may be across the width of the hybrid film 20 ' be uniform or thicker at the corners than in the central area.

The metal film 124 used in packaging typically comprises aluminum. The thickness of the metal film is in the range of 100 to 400 Å.

EXAMPLES

1. CAPACITORS

capacitors use thermoplastic thin-film dielectric polymers at low temperature, such as polypropylene (PP), polyethylene terephthalate (PET), polycarbonate, Polyethylene-2,6-naphthalate, polyvinylidene difluoride (PVDF), polyphenylene oxide and polyphenylene sulfide, either metallized or between metal foil electrodes held. Metallized film capacitors are becoming widely used used in a wide range of electrical and electronic equipment, those with engine operation and engine starting circuits for air-conditioning equipment, ballasts of fluorescent lamps and high intensity lamps, Power units, Telecommunications equipment, instrumentation and medical electronics include. In many of these applications metallized capacitors for storing energy by correcting the power factor used in one circuit and in others they are more specific to performing Functions such as timing, filtering and decoupling, used. The Advantages of metallized film over film-foil capacitors include lower volume, weight, cost and higher reliability due to the self-healing properties of the metallized films. The low temperature metallized film dielectrics are due to their low dielectric loss in a variety of High voltage and high frequency capacitor applications use.

However, a disadvantage is a lower current capability due to the thin metallized electrodes deposited at low temperature thermoplastic dielectrics such as PP, PET and polycarbonate are. In particular, reliability problems arise when metallized capacitors are forced to withstand high intensities of pulsed or alternating current. The present invention relates to the production of a hybrid film having improved mechanical and thermal properties that improve capacitor performance and reliability.

The The following discussion is on low-level AC applications Loss directed the deposition of an acrylate film on one Polypropylene film and the subsequent metallization below Formation of a metallized thin-film capacitor include. However, those skilled in the art will readily appreciate that these Teaches extending to other base polymer films for other applications can be.

Over 100 acrylate monomer materials were polymerized and tested for dielectric constant and loss factor as a function of temperature and frequency and oil and water surface wetting. Some of these materials were obtained from different suppliers as a source, others were formulated using proprietary mixtures of commercially available monomers, and some were molecularly synthesized. The tested acrylate polymer materials include the following: 2,2,2-trifluoroethyl acrylate, 75% 2,2,2-trifluoroethyl acrylate / 25% C ₁₉ diol diacrylate, 50% acrylonitrile / 50% C ₂₀ diol diacrylate, dimeroldiacrylate, 50% acrylonitrile / 50 % C ₁₉ diol diacrylate, Erpol 1010 diacrylate, 50% hexanediol diacrylate / 50% C ₂₀ tri-diacrylate, 50% 2,2,2-trichloroacrylate / 50% C ₁₉ diol diacrylate, 75% 2,2,2-trifluoroethyl acrylate / 25% C ₁₉ diol diacrylate, 50% octanediol diacrylate / 50% 2-cyanoethyl acrylate, 67% 2,2,2-trifluoroethyl acrylate / 33% C ₂₀ triol triacrylate, lauryl acrylate, trimethylolpropane triacrylate, ethoxyethoxyethyl acrylate, pentaerythritol tetraacrylate, neopentyl glycol diacrylate, octyldecyl acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, Octanediol diacrylate, 1,8-alkoxylated aliphatic acrylate, decanediol diacrylate, ethylene glycol diacrylate, isobornyl acrylate, butanediol diacrylate, 93% hexanediol diacrylate / 7% KENSTAT q100, 95% hexanediol diacrylate / 5% chlorinated polyester diacrylate, trimethylolpropane ethoxylate tr iacrylate, trimethylolpropane propoxylate triacrylate, neopentyl glycol propyl acrylate diacrylate, bisphenol A ethoxylate diacrylate, alkoxylated aliphatic diacrylate ester, 50% 2-cyanoethyl acrylate / 50% C ₁₉ diol diacrylate, 92% trimethylolpropane triacrylate / 8% acrylonitrile, 50% isobornyl acrylate / 50% pentaerythritol triacrylate, 83% trimethylolpropane triacrylate / 17 % FLUORAD FX189, 50% acrylonitrile / 50% trimethylolpropane triacrylate, 70% trimethylolpropane triacrylate / 30% acrylonitrile, 40% FLUORORAD FX189 / 60% trimethylolpropane triacrylate, 70% hexanediol diacrylate / 30% isobornyl acrylate, 50% hexanediol diacrylate / 50% isobornyl acrylate, 12.5% aliphatic urethane triacrylate / 87.5% hexanediol diacrylate, 31% KENSTAT q100 / 69% _C14 -Dioldiacrylat, 69% C ₁₄ -Dioldiacrylat / 31% acrylonitrile, 80% C ₁₄ -Dioldiacrylat / 20% KENSTAT q100, 94% trimethylolpropane propoxylate triacrylate / 6% KENSTAT q100, 50% trimethylolpropane triacrylate / 50% acetonitrile, 70% trimethylolpropane triacrylate / 30% acetonitrile, 88% phenol ethoxylate monoacrylate / 12% acetonitrile, 80% C ₁₄ diol diacrylate / 20% acetonitrile, 80% C ₁₄ diol diacrylate / 20% KENSTAT q100, 12% trimethylolpropane triacrylate / 88% isobornyl acrylate, 69% C ₁₄ diol diacrylate / 23% KENSTAT q100 / 8% trimethylolpropane triacrylate, 33% acetonitrile / 33% Polyaminacrylat / 34% isobornyl acrylate, 75% aliphatic amine acrylate / 17% KENSTAT q100 / 8% trimethylolpropane triacrylate, 80% C ₁₄ -Dioldiacrylat / 20% FLUORAD FX189, 80% phenol ethoxylate monoacrylate / 20% pentaerythritol triacrylate, 80% hexane diol diacrylate / 20% acrylonitrile, 70% Hexanediol diacrylate / 15% acrylonitrile / 15% trimethylolpropane triacrylate, propoxylated glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, caprolactone acrylate, 90% alkoxylated trifunctional acrylate / 10% beta carboxyethyl acrylate, 90% polyethylene glycol 200 diacrylate / 10% pentaerythritol di-tritetraacrylate, 75% hexanediol diacrylate / 25% KenReact LICA 44, 50% pentaerythritol tetraacrylate / 50% hexanediol diacrylate, pentaerythritol polyoxyethylene tetraacylate, tetrahydrofurfuryl acrylate, 25% KENSTAT q100 / 75% hexanediol diacid rylate, 50% tetrahydrofurfuryl acrylate / 50% polyethylene glycol 200 diacrylate, 88% tetrahydrofurfuryl acrylate / 12% trimethylolpropane triacrylate, 88% caprolactone acrylate / 12% trimethylolpropane triacrylate, EBECRYL 170, 80% EBECRYL 584/20% beta-carboxyethyl acrylate, 88% tetrahydrofurfuryl acrylate / 12% beta carboxyethyl acrylate, 88% EBECRYL 170/12% beta carboxyethyl acrylate, aliphatic polyester hexaacrylate oligomer, aliphatic urethane diacrylate, tripropylene glycol diacrylate, hexanediol diacrylate, 88% isobornyl acrylate / 12% beta-carboxyethyl acrylate, 90% polyethylene glycol 200 diacrylate / 5% isobornyl acrylate / 5 % Pentaerythritol triacrylate, 82% polyethylene glycol 200 diacrylate / 12% hexanediol diacrylate / 6% trimethylolpropane triacrylate, 75% tetrahydrofurfuryl acrylate / 15% hexanediol diacrylate / 5% trimethylolpropane triacrylate / 5% oligomer, 44% polyethylene glycol 200 diacrylate / 44% acrylonitrile / 12% hexanediol diacrylate , 70% C ₁₄ diol diacrylate / 30% aliphatic urethane acrylate oligomer, trimethylolpropane ethoxylate triacrylate, and 50% PHOTOM ER 6173/50% hexanediol diacrylate 50%. Notes: KENSTAT q100 and KenReact LICA 44 are trade names of Kenrich Corp .; FLUORAD FX 189 is a trade designation of 3M Industrial Chemical Corp .; EBECRYL 170 and EBECRYL 184 are trade names of UCB Radcure Corp .; and PHOTOMER 6173 is a trade designation of Henkel Corp.

Several Acrylate polymers have been used as candidate materials for AC capacitor models identified. These are polymers with a low loss factor (DF) with DF <0.01, i.e. <1%, and one permittivity (κ) in the area 2.5 <κ <4.0.

PP-acrylate hybrid films were produced using a production size vacuum metallization chamber, adjusted backwards became a deposit of acrylate coatings in a line to enable with the metallization process. PP films of 6 μm, 8 μm, 12 μm and 19 μm were initially used with treated with a gas plasma and then with acrylate polymer films with Thicknesses of 0.2 to 1.0 microns coated. The dielectric characterization of small area embossing capacitors with PP films (control) and hybrid films showed that the PP acrylate films excellent ampacity, higher resistance to one Degradation due to partial discharges (corona) and one to PP films same thickness same or higher Had breakdown voltage.

One Another advantage that was unexpected was the improved corrosion resistance the metallized aluminum electrodes, if these on the acrylate coating instead of being deposited on the PP film. This is very important since it is thinner use Allows aluminum layers, what the self-healing properties of hybrid film capacitors elevated.

Several Condenser models were full size produced and tested. Capacitors with data 8 μF / 330 V AC, 0.1 μF / 1200 V DC and 0.1 μF / 2000 V DC were prepared using acrylate-coated PP films of 6 μm, 12 μm or 19 μm built. Short-time current, moisture and breakdown voltage tests showed that the acrylate-PP hybrid capacitors the performance of stamping capacitors small area followed. This means, the hybrid film capacitors had a significantly higher power as the PP control capacitors. At a decisive high dV / dt test, with pulses of 5000 V with a rise time of 1000 V / 50 ns were applied, the 0.1 μF / 2000 V capacitors showed a much higher Performance than commercial capacitors, the double metallized PET film electrodes (for higher Current carrying capacity) and a dielectric of the same thickness used. The commercial capacitors showed degradation after 2400 pulses Failure while no degradation occurred in the hybrid film capacitors of 19 microns. In fact they were the hybrid film capacitors of 12 μm (0.1 μF / 1200 V), which are less than the half of the volume of Kondenstoren of 19 microns, the commercial Also consider capacitors if they were tested under the same conditions. A comparison of PP capacitors of light-emitting devices of 12 μm with acrylate PP film capacitors of 12 μm using pulses of 3000 V showed no degradation in the Hybrid film capacitors while the performance of conventional Capacitors from two different manufacturers of significant Removal up to complete Failure varied.

Large quantities Acrylic hybrid films were coated, metallized and submerged Use of conventional Winding machines wound to capacitors. The acrylate PP film let himself go like any other capacitor film over the different process steps handle. Because the acrylate polymer is in line with the metallization and can be deposited in the same vacuum chamber, are the additional Labor costs minimal. The basic acrylate monomers are at a cost Available from $ 3 / lb to $ 4 / lb and at a thickness of 1 μm are the extra Material costs minimal.

A. Hybrid film production process development

Acrylate-PP hybrid films were produced using 6 μm, 8 μm, 12 μm and 19 μm PP films readily available. Rolls of 32 cm wide films that were at least several thousand feet long (typical size for low metallization passes) were used. The apparatus used in the coating process is shown schematically in FIG 1 shown. The liquid monomer was removed from the container 40 that is outside the vacuum chamber 12 was positioned in the flash evaporation device 28 pumped. The liquid monomer was prepared using the ultrasonic atomizer 42 at the top of the evaporator 28 was positioned, atomized to microdroplets. The evaporation device 28 was maintained at a temperature above the boiling point of the liquid but below its decomposition point. This caused flash evaporation of the monomer before it was cured. The molecular vapor came out at supersonic speeds and condensed on the film 20 which is in intimate contact with the cooled rotating drum 16 was standing. The condensed thin film deposit then moved in front of the electron gun 30 where it was polymerized.

Examples for suitable Acrylates, when performing of the invention include isobornyl acrylate, hexanediol acrylate and tripropylene glycol diacrylate suitable for rapid cure viscosity and good adhesion were formulated on the PP film. These acrylates all have one Loss factor of less than 0.01.

• 1. Trommeltemperatur: Gute Filme können in einem Temperaturbereich von Raumtemperatur bis –20°C hergestellt werden. Die untere Temperatur schien die Kondensationsrate bei einigen Monomeren etwas zu erhöhen, bei anderen jedoch nicht. Es wurde geschätzt, dass die Verweilzeit des Films auf der Trommel nicht ausreichend war, um viel von der Trommeltemperatur auf die obere Oberfläche des Films zu übertragen. Infolgedessen hatte ein Unterschied der Trommeltemperatur keine größere Wirkung auf die Monomerkondensationsrate.
• 2. Trommelgeschwindigkeit: Gute Filme wurden mit Trommeloberflächengeschwindigkeiten beliebig im Bereich von 50 bis 1000 Fuß/min (25 bis 500 cm/s) produziert.
• 3. Strahlendosis: Das Beschleunigungspotential betrug 12 KeV und der dem Monomer zugeführte Strom betrug etwa 2 mA zur Härtung von Monomerfilmen einer Dicke von 1 μm.
• 4. Endmonomergemisch: Die meisten der Monomergemische, die verarbeitet wurden, ergaben bei Betrachtung von Parametern wie Gleichförmigkeit, Härtungsgrad und Adhäsion an dem PP-Film Beschichtungen guter Qualität. Ein Beispiel für ein geeignetes Monomergemisch umfasste ein Gemisch von 70% Hexandioldiacrylat, 20% Isobornylacxrylat uns 10% Tripropylenglykoldiacrylat.
• 5. Plasmabehandlung vor Acrylatablagerung: Der PP-Film wurde vor der Ablagerung des Monomerdampfes aus den folgenden Gründen plasmabehandelt:
• a. Die PP-Filmoberfläche hat Sauerstoff und Feuchtigkeit absorbiert, die in die Polymerisation des Acrylatmonomers eingreifen. Sauerstoff ist ein Fänger freier Radikale, der durch den Elektronenstrahl erzeugte freie Radikale neutralisiert, wodurch der Polymerisationsprozess gehemmt wird.
• b. Die Plasmabehandlung ätzt und reinigt die Filmoberfläche von einem Rückstand mit niedrigem Molekulargewicht, der durch den Koronabehandlungsprozess erzeugt wurde. Dies verbessert die Benetzung des Films durch das Monomer, was zu einer gleichförmigeren Beschichtung führt.
• 6. Plasmabehandlung nach Ablagerung des Acrylatpolymers: Dies ist eine Nachbehandlung, die zur Verringerung der statischen Aufladung auf dem beschichteten Film und auch Vervollständigung des Polymerisationsprozesses auf der Acrylatoberfläche verwendet wurde. Diese Verfahrensstufe verringerte die "Klebrigkeit" an der Acrylat-PP-Aufwicklungsrolle.

Several large rolls of a PP film of 6 μm and 8 μm were used under different conditions coated until a set of parameters giving a well cured uniform coating was obtained. The main process parameters are the following:

• 1. Drum Temperature: Good films can be made in a temperature range from room temperature to -20 ° C. The lower temperature appeared to slightly increase the condensation rate for some monomers, but not for others. It was estimated that the residence time of the film on the drum was insufficient to transfer much of the drum temperature to the upper surface of the film. As a result, a difference in drum temperature had no greater effect on the monomer condensation rate.
• 2. Drum Speed: Good films were produced at drum surface speeds anywhere in the range of 50 to 1000 feet per minute (25 to 500 cm / sec).
• 3. Radiation Dose: The acceleration potential was 12 KeV and the current supplied to the monomer was about 2 mA for curing monomer films of 1 μm thickness.
• 4. Final Monomer Mixture: Most of the monomer blends that were processed gave good quality coatings when considering parameters such as uniformity, degree of cure and adhesion to the PP film. An example of a suitable monomer mixture included a mixture of 70% hexanediol diacrylate, 20% isobornyl acrylate, and 10% tripropylene glycol diacrylate.
• 5. Plasma Treatment Before Acrylate Deposition: The PP film was plasma treated prior to deposition of the monomer vapor for the following reasons:
• a. The PP film surface has absorbed oxygen and moisture which interfere with the polymerization of the acrylate monomer. Oxygen is a free radical scavenger that neutralizes free radicals generated by the electron beam, thereby inhibiting the polymerization process.
• b. The plasma treatment etches and cleans the film surface from a low molecular weight residue produced by the corona treatment process. This improves the wetting of the film by the monomer, resulting in a more uniform coating.
• 6. Plasma treatment after deposition of the acrylate polymer: This is an aftertreatment used to reduce the static charge on the coated film and also complete the polymerization process on the acrylate surface. This process step reduced the "stickiness" on the acrylate PP take-up roll.

B. Evaluation of hybrid films using small area films

The Hybrid films were first using embossing capacitors small area and then coiled full size capacitors became further Rating made. stamp capacitors were used to evaluate the dielectric strength, ampacity, Decomposition of polymer films by partial discharge (corona) and corrosion resistance the metallized electrodes used.

1. Dielectric constant and loss factor

The Acrylate coating has little influence due to its small thickness on both and the DF of hybrid films. Dependent on of the particular hybrid was the dielectric constant of the acrylate PP films up to 7% higher as that of a pure PP movie.

2. DC breakdown strength

This measurement was made to ensure that the hybrid film had a dielectric strength of at least the same height as the original PP film + an additional amount due to the acrylate coating. The breakdown measurements on the films were made using a dry double metallized and non-contact measurement technique performed under high vacuum (<10 ^-4 torr) to eliminate partial discharges and surface flashovers. The breakdown system was built in a turbomolecular pumped stainless steel chamber. Metallization masks were designed and fabricated to allow metallization of small area (6,25 cm ² (1 square inch)) emboss capacitors for breakdown measurements. Electrode contact was via metallized poles that were out of the active area to prevent film damage. The voltage increase took place at 500 V / s. For each breakdown measurement set out below, at least 18 embossing capacitors were tested to ensure that the data is statistically significant.

The results of the DC punch tests of 6 μm and 8 μm films coated with 0.5 μm acrylate polymer are shown in Table I. The acrylate polymer is prepared by electron beam curing a monomer film of 70% hexanediol diacrylate, 20% isobornyl acrylate, and 10% tripropylene glycol diol acrylate working in vacuo using the in 1 deposited experimental device produced. The PP film was first plasma treated using an argon gas plasma and the acrylate monomer was flash evaporated on the treated surface.

TABLE I

The Breakdown voltage of the control and acrylate hybrid films was determined by Metallization electrodes of one square inch at opposite Pages of the films measured. Each measurement represents the mean of at least eighteen individual breakdown measurements Data in Table I show that the acrylate-coated PP films have a dielectric strength that is 10% higher than that is the control PP movie. With regard to the coating thickness about 0.5 μm is, the dielectric strength of acrylate PP films is equal to or higher than the PP movies. Similar Measurements on individual acrylate layers showed that the dielectric strength of 1 μm thick films 20 to 24 kV / mil, which is equal to or higher than that's a PP movie.

3. current carrying capacity

It is known that due to the low melting point of a PP film, metallized PP capacitors become very unreliable in heavy current applications due to thermal damage to the termination. The current at Termination I produces ² R losses (R = equivalent series resistance, ESR), which increases the temperature, which in turn damages the termination and increases the ESR. This process eventually leads to catastrophic failure. Life test data showed that many conventional PP capacitor models have marginal current carrying capacity. For this reason, in some heavy current models, double metallized paper or a double metallized PET film having a higher melting point than PP is used to guide the flow. These PET / PP models are inefficient and lead to costly capacitor products.

To simulate the current flow from the sprayed termination to the metallized film and the ability of the film to conduct high currents without thermal damage, a simple test has been developed to maximize the energy that a metallized film can dissipate before thermal failure. developed. Current was forcibly passed through a portion of a metallized film and the energy (IxV) was increased until the converted heat forced a failure of the film. The solid device had 1.27 cm (1/2 inch) wide contact electrodes spaced 12.7 cm (5 inches) apart. AC voltage was applied to the electrodes and the current in the circuit was recorded. The stress was increased until the energy loss thermally degraded the metallized film to the point of failure. In the films that were tested, the failure was an open circuit caused by melting the PP film at a point near the center of the 12.7 cm (5 inch) strip. Table II shows the average energy to failure (eight samples were tested for each condition) for both coated and uncoated 8 μm polypropylene. The acrylate polymer was prepared by electron beam curing a monomer film of 70% hexanediol diacrylate, 20% isobornyl acrylate, and 10% tripropylene glycol diacrylate, which was vacuum dried using the in 1 deposited experimental device produced. The PP film was first plasma treated using an argon gas plasma and the acrylate monomer was flash evaporated on the treated surface.

TABLE II

The Results show that the coated films have a higher heat capacity, which varies from 4% to 63%. The variation is mainly based on the thickness of the acrylate coating.

It is interesting to note that, although the coated films at significantly higher Energy levels failed, they did not cause so much deformation and shrinkage as the pure films showed. The higher heat capacity of the hybrid films was one key task in this work and it is clear that thin coatings of high temperature acrylate films a significant importance in the thermal properties of Have PP.

4. Stability across from a degradation due to partial discharges (corona)

one the most common Mechanisms of a failure at high voltage (V> 300 V DC) film capacitors is a damage of the polymer dielectric due to partial discharge activity (corona) in the capacitor windings. The partial discharges or corona pulses are generated in Zwischenelektrodenbereichen, the sufficiently large air gaps have to maintain a certain degree of ionization. The high-temperature corona pulses can, although they can physically move around, the polymer dielectric break down and cause a breakdown. Dry metallized Capacitors are for a coronary damage particularly sensitive, especially at the outer and innermost windings, which are looser than the rest of the roll. Metallized capacitors, the electrodes have a fairly high resistance (3 to 8 ohms / sq) have good self-healing properties and the corona-induced Losses lead to a certain capacity loss without further damage of the capacitor. Capacitors with electrodes from 2 to 3 ohms / sq have worse loss characteristics. The preserved high corona levels can to a larger capacity loss, increased Loss factor, higher Leakage current and frequent cause catastrophic failure.

The resistance to the damaging thermal effects of the corona pulses increases as the thermal stability of the polymer film increases. Control polyvinylidene difluoride (PVDF) and polypropylene (PP) films were tested for corona degradation along with PVDF / plasma / acrylate and PP / plasma / acrylate hybrid films. The acrylate polymer was prepared by electron beam curing a monomer film of 70% hexanediol diacrylate, 20% isobornyl acrylate, and 10% tripropylene glycol diacrylate, which was vacuum dried using the in 1 deposited experimental device produced. The PP film was first plasma treated using an argon gas plasma and the acrylate monomer was flash evaporated on the treated surface.

The acrylate PVDF hybrid was used because a PVDF film coated the capacitor dielectric with the highest energy density, which is commercially available, and an acrylate-PVDF hybrid can present some unique favorable product properties. Furthermore, the PVDF film has about the same melting point as PP. The PVDF embossing capacitors were liquid soaked and tested at 1200 VAC. The PP capacitors were dry and tested at 350 VAC. This test was an accelerated coronary test where the level of partial discharges reflected either poor impregnation (impregnated cap) or loose outer windings in a dry capacitor. So far, several embossing capacitors have been tested and the results are shown in Table III.

TABLE III

As from Table III, the hybrid films had about one Magnitude longer Time to failure. This can change the reliability of the capacitors increase significantly. In the case of a capacitor of the pulse type, this can be a large number additional Represent pulses before failure due to corona degradation.

5. corrosion resistance

loss of capacity due to electrode corrosion is the most common failure mechanism in metallized capacitors. The corrosion resistance of aluminum electrodes based on control PP and PP / plasma / acrylate films were deposited, was tested. The corrosion stability of with Aluminum metallized PP and PP / Plasma / Acrylic films were through Measuring the change of the electrical resistance of a metallized strip of 12.7 cm × 2.5 cm (5 inches by 1 inch) after exposure in a temperature / humidity environment from 70 ° C / 85% relative humidity tested. The strips of 12.7 cm (5 Inch) were made large Material rolls, which are also fuller for making capacitors Size used were cut out. To ensure that every measurement (especially when corrosion of the electrode starts) a good Electrode contact was made on both ends of the strip of 12.7 cm (5 inches) a thicker aluminum overlay deposited.

The control PP and hybrid films were produced from the same PP film roll by plasma treatment and acrylate coating of one half of the roll (32 cm wide and 3048 m (10,000 feet) long) and then metallizing the entire roll in a single metallization pass. 2 Figure 12 shows the change in electrical resistance as a function of time for an aluminum metallized control PP film of 6 μm (plot 52 ) next to a PP / plasma / 1 μm acrylate film (curve 50 ). The acrylate polymer was replaced by electro Radiation hardening of a monomer film of 70% hexanediol diacrylate, 20% isobornyl acrylate and 10% tripropylene glycol diacrylate, which is applied in vacuo using the in 1 deposited experimental device produced. The PP film was first plasma treated using an argon gas plasma and the acrylate monomer was flash evaporated on the treated surface. The data show that the metallized aluminum electrodes on the hybrid films have excellent corrosion resistance.

The surface properties of the polymer film in the structural and chemical stability of the metallized electrodes play a major role. Several investigations have been made in the past carried out, that show a surface treatment the polymer films prior to metallization the adhesion and corrosion resistance the aluminum electrodes improved. Film crosslinking, polar chemical functionalities and the absence of low molecular weight material Parameters that the acrylate surface favor. Furthermore, a PP film is usually always before the metallization corona or flame treated. This is done in a line with the Film manufacturing process. Subsequent exposure to environmental conditions leads to Moisture adsorption by through the treatment process formed carboxyl, carbonyl and Hydroxy groups. The adsorbed moisture reacts with the aluminum deposit and worsens their chemical stability.

The The above tests show that the hybrid acrylate films have a surface with unique surface properties that have the chemical resistance of vapor-deposited Increase aluminum metal coatings.

C. Evaluation of hybrid films using capacitors of full size

Full size capacitors based on a 330V AC model were fabricated using 8 μm control PP films and a PP / plasma / 0.7 μm hybrid acrylate film. The acrylate polymer was prepared by electron beam curing a monomer film of 70% hexanediol diacrylate, 20% isobornyl acrylate, and 10% tripropylene glycol diacrylate, using vacuum in 1 deposited experimental device produced. The PP film was first plasma treated using an argon gas plasma and the acrylate monomer was flash evaporated on the treated surface. The capacitors were wound up in solid hex cores and had a cylindrical shape.

capacitors were full size built in the same conditions as the films of small area and on electrode corrosion resistance in terms of the lifetime tested. Instead of determining the capacity change was due to the short test period, the optical density of Electrodes measured. In this way, the aluminum oxidation could be detected, even if the electrode was conducting, leading to none loss of capacity led. The optical density was first on the rollers used to make the capacitors, measured. After the test, the capacitors were unwound and the optical density of the metallized film at the outer part of the roll in one fixed distance measured from the end of the winding. The results of this test are shown in Table IV. Four sets of capacitors were under Use of a control PP film and PP / plasma / 0.7 μm hybrid acrylate film coated with thin Aluminum (optical density 1.25 and 1.51, in Table IV as (1) and thicker aluminum (optical density 1.68 and 1.76, in Table IV as (2)).

TABLE IV MODIFICATIONS OF THE OPTICAL DENSITY OF ALUMINUM METALLIZED CAPACITOR FILMS OF PP AND PP / PLASMA / 0.7 μm ACRYLATE FILMS BASED ON CORROSION IN A SURROUNDING 70 ° C AND 85% RELATIVE HUMIDITY.

The results in Table IV show that the corrosion properties of control PP and acrylate-PP hybrid films are basically the same as those of the small area films when wound into capacitor rolls (Hybrid (1) is the same film material used in small area test pieces was tested, see 2 ). That is, metallized capacitors wound with acrylate hybrid films experience less electron corrosion than similar parts produced with control metallized PP films.

This is a significant advantage for the hybrid films. The improved corrosion resistance of the metallized Electrodes enabled the use of this product in applications where the capacitors higher Humidity and temperature are exposed.

One Radio frequency test with high current / low voltage has been developed to evaluate the ampacity of the capacitor termination. The current through the capacitors was determined by varying the voltage amplitude changed the high frequency signal. After testing several capacitors, set a set of conditions to determine the capacitor termination in a measurable Grade deteriorated, were both pure PP and hybrid film capacitors tested. The test data shown in Table V show that capacitors, those with the acrylate-PP hybrid film dielectrics better parameter stability than sister units that were built with control PP movie were produced.

TABLE V LOSS FACTOR AND ESR OF CAPACITORS BUILT WITH PP FILM AND ACRYLATE PP HYBRID FILM. YOU WILL BE TESTED AT 40 kHz BEFORE AND AFTER THE STRONGSTROM TEST. INSTALL SETTING

AFTER 10 MIN 25 kHz 50 A PEAK VALUE AT 60 V PEAK VALUE

AFTER FURTHER 5 MIN 25kHz 75A PEAK VALUE AT 85V PEAK VALUE

The Current carrying capacity of the full size capacitors is in line with the power or energy dissipation characteristics metallized films of small area (Table IV). It is further interesting to note that the hybrid film capacitors fuller Size with hybrid (2) movie (see Table IV), which does not have the highest or best energy loss properties showed, were manufactured. This suggests that with optimized Hybrid films built capacitors far better properties than the capacitors tested could have.

Capacitors with a capacitance of 0.1 μF were prepared using 19 μm PP / Plasma / 1.0 μm acrylate (referred to as Hybrid A in Table VI) and 12 μm PP / Plasma / 1.0 μm acrylate (in Table VI as Hybrid B) manufactured. These capacitors were arbitrarily assigned 0.1 μF / 2000 V DC and 0.1 μF / 1200 V DC, respectively. The acrylate polymer was prepared by electron beam curing a monomer film of 70% hexanediol diacrylate, 20% isobornyl acrylate, and 10% tripropylene glycol diacrylate, which was vacuum dried using the in 1 deposited experimental device produced. The PP film was first plasma treated using an argon gas plasma and the acrylate monomer was flash evaporated on the treated surface.

The Capacitors were equipped with commercial power capacitors of the Prior art, which, although the designation 0.1 μF / 1200 V also had a PP dielectric of 19 microns and double metallized Polyester (PET) film electrodes used to power the power to lead, compared. These capacitors were about the same size as the metallized capacitors of 0.1 μF of the hybrid (A) film and more as the double volume of the capacitors of 0.1 μF of hybrid (B).

All Capacitors were designed using 5000V pulses dV / dt of 1000 V / ns tested. The capacity and ESR were using a conventional electronic capacitance bridge measured. The capacity and ESR be in the beginning with the capacity and ESR after the test are compared in the following Table VI.

TABLE VI. VOLTAGE AND ELECTRIC LOAD COMPENSATION OF COMMERCIAL PP CAPACITORS OF THE PRIOR ART AND CAPACITORS BUILT WITH ACRYLATE HYBRID FILMS ACCORDING TO THE PRESENT INVENTION Commercial Capacitor

Present invention, 19 μm hybrid (0.1 μF / 2000 V)

Present invention, 12 μm hybrid (0.1 μF / 1200 V)

It it can be seen that the 0.1 μF / 2000 V DC (hybrid (A)) model the same as the commercial model Size in one very big Measurements surpasses. Indeed show the data that all except two of the commercial capacitors failed while none that produced by the process of the present invention Capacitors showed a significant degradation. With regard according to the present Invention prepared 0.1 uF / 1200 V (hybrid (B)) capacitors (which are less than half of the Size of the commercial Possess capacitors) show the data that, although these capacitors on average, their properties were better than the commercial capacitors of the prior art were.

II. FOOD PACKAGING FOILS

at Packaging applications are barrier films for the separation of products, like food and electronic components, from environments that reduce product life, of particular interest. such Barrier films can either using films that contain the barrier in the film is installed, or by applying a coating to a Movie can be achieved. The barrier coating can be either transparent being, for example, comprising oxide materials, or opaque or semitransparent, for example comprising metals.

The renewal storage time at competitive cost is an ongoing one Challenge for Film producers, Metallisierungsbetriebe and laminators. Especially acts for Food applications of the metallized film or the metallized Foil as (a) oxygen and moisture barrier to food fresh and crispy, (b) light barrier to reduce rancidity in fatty foods and (c) aroma barrier to keep the original flavor intact. Other requirements include the processability of the metallized Films, abrasion resistance, mechanical robustness, reliability and costs.

A. Opaque metallized barrier films

The Barrier properties of metallized aluminum films almost hang Completely from the integrity of metallized aluminum layer. The quality of the metallized layer depends on Defects on the surface of the polymer film. Size Defects manifest themselves mainly in the form of pinholes in Metallization visible with the optical microscope. Pinhole defects are usually attributed to Particles on the film surface and attrition of the aluminum on film fibers and other surface protrusions caused by antioxidants and lubricants. These Features speckle the surface landscape the movies and are for a special film supplier and a manufacturing process characteristic. Although the number and size of pinholes is the permeability dominated by oxygen through the film, there are more microstructural defects, the ultimately possible Barrier for determine a given movie. Microstructural defects can be several Have shapes, the microwell holes, microcracks, and microareas of very thin Include aluminum. These defects can be traced to properties of the substrate film containing the base film chemistry and the method of preparation, Parameters, such as the molecular weight of the film used to make the film used resin, additives for the Resin, process conditions and surface treatment of the film. An improved lock feature can be achieved by minimizing both Big- as well as microstructure defect density on the film surface become.

Several Materials were for use in the production of metallized Films with high barrier properties. A key requirement is that the monomer and of course the polymer coatings must have a small amount of volatile components in order to ensure that the packaging material does not smell. In order to qualify polymer materials, an "aromatics" standard was performed, and many of the polymer materials that were tested passed the Test. A deodorized version of tripropylene glycol diacrylate was arbitrarily to carry out chosen by oxygen barrier tests.

For opaque High Oxygen Barrier Packaging (Potato Chips Bag) The industry standard is a polypropylene film (PP) that comes with a thin Layer of aluminum (Al) is metallized. The barrier material development included the following models of metallized PP and acrylic hybrid films.

1. PP / Plasma / Al / Acrylic / Plasma

The acrylate polymer was prepared by electron beam curing of a tripropylene glycol diacrylate monomer film, which was vacuum dried using the in 1 deposited experimental device produced. The thickness of the acrylate polymer was 1.0 μm. The PP film was first plasma-treated using a gas plasma produced by an Ar / N ₂ gas mixture at a 10% / 90% ratio, and aluminum was applied on top of the plasma-treated surface. The acrylate polymer was applied to the top of the thin aluminum metal to prevent needle hole formation due to abrasion of the film surface on rollers in the vacuum chamber and subsequent processes such as cracking and lamination. The structure is in 3D specified.

The plasma treatment functionalization of the PP film resulted in higher nucleation rates of the aluminum and a finer crystal structure. The formation of finer aluminum crystallites was determined using X-ray diffraction (XRD) analysis. Specifically, the metallized films were tested using a Scintag XRD system, which showed that the 2.344 cps peak of aluminum for the plasma-treated film was at least three times less intense and about twice as wide than the untreated metallized film. Also, transmission electron microscopy (TEM) and electron diffraction analysis performed on a Hitachi TEM showed that the crystals in the aluminum deposited on the plasma-treated PP film were much smaller with very broad diffraction rings (as compared to the control PP-deposited aluminum) , The finer aluminum crystallites result in a more flexible metal film that resists microcracking during stretching. This was done by monitoring the elektri The resistance of a metallized film while the film was stretched at a fixed speed was determined using a computer controlled system. For a metallized film, microcracking of the metal layer leads to an increase in its electrical resistance. 4 shows the change in resistance to percent elongation for a control PP / aluminum film (curve 54 ) and PP / plasma / aluminum (curve 56 ). As can be seen, the aluminum deposited on the functionalized plasma-treated surface has a significantly higher microcracking resistance than the control.

2. PP / Plasma / Acrylic / Al

The acrylate polymer was prepared by electron beam curing of a tripropylene glycol diacrylate monomer film, which was vacuum dried using the in 1 deposited experimental device produced. The thickness of the acrylate polymer was 1.0 μm. The PP film was first plasma treated using a gas plasma produced by an Ar / N ₂ gas mixture at a 10% / 90% ratio, and the acrylate monomer was flash evaporated on the treated surface. The acrylate was applied under the aluminum layer to smooth the rough surface of the PP film and also to produce a thermally and mechanically excellent substrate. As shown in the section "Capacitor" above, this leads to higher corrosion resistance of the aluminum layer. The structure is in 3B specified.

Further enthäkelt the surface of PP film low molecular weight material that is degraded from PP PP and the movie while the production of added lubricants. It was discovered that these low molecular weight species will flow again if they are caused by the evaporation sources and the condensation of the aluminum deposit generated heat get abandoned. The re-flow prevents nucleation of aluminum atoms on the surface of these sites, thereby Pinholes generated which are the moisture and oxygen barrier properties deteriorate. This effect is eliminated or minimized when the high temperature acrylate polymer is deposited on the PP surface and then metallized.

3. PP / Plasma // Acrylic / Al / Acrylic / Plasma

The acrylate polymer was prepared by electron beam curing of a tripropylene glycol diacrylate monomer film, which was vacuum dried using the in 1 deposited experimental device produced. The thickness of the acrylate polymer was 1.0 μm. The PP film was first plasma treated using a gas plasma produced by an Ar / N ₂ gas mixture at a 10% / 90% ratio, and the acrylate monomer was flash evaporated on the treated surface. This is a combination of the two systems above. Other combinations with a second layer of aluminum are also possible but less cost effective. The structure is in 3C specified.

Around making hybrid film production more economically attractive can be worse qualities of PP films (lower cost), which in metallization oxygen transmission rates (OTRs) range from 3 to 10, compared to higher quality films, the OTRs in the range of 1 to 3, can be used. The data in Table VII below shows that the OTR of control films (PP / Al) from 6.17 to 0.07 using the above described hybrid film models can be reduced. All OTR and MVTR barrier measurements reported here were from a Third party using commercial equipment. Considering, that the hybrid films in the same metallization, in which the control films were produced, and with low additional Costs can be produced The OTR values of hybrid films provide an unpredictable level of improvement and they are commercially available Far superior to films or foils.

TABLE VII OXYGEN PURITY RATE (OTR) OF METALLIZED CONTROL PP (PP / Al) AND ACRYLATE / PP HYBRID FILMS

It should be noted that in the case where the acrylate polymer was deposited directly on the polypropylene (the above configurations 2 and 3), the polypropylene was plasma-treated. It has been found that the plasma treatment is advantageous for two reasons: (a) it removes adsorbed air and moisture from the surface of the PP film, which enhances the degree of crosslinking on the PP / acrylate interface, and (b) functionalizes the PP Film, which allows wetting by the acrylate monomer. Several gases were used for the plasma treatment process, including Ar, N ₂ , O ₂ , Ne, CO _2, and mixtures thereof. Ar and N ₂ in a 10% / 90% mixture gave a very effective mixture, as determined by wetting and uniformity of the polymer layer, and this also gave mixtures with 5% O ₂ . Another effective gas mixture comprises 9.9% Ne and 0.1% Ar and a mixture thereof with 10% N ₂ or 5% O ₂ or 5% CO ₂ . The long-lived metastable states in the Ne atom enhance the ionization state of the mixture and significantly increase the ionization current and surface treatment. Another effective mixture is 96% CF ₄ and 4% O ₂ .

It It was also found that at times after the hybrid film wound into a roll, a certain degree of "blocking" or stickiness developed because the back of the polypropylene film deposited on this one soft copolymer layer has, which used for thermal sealing of the plastic bag becomes. The stickiness was the result of the combined effect a partial hardening on the surface the acrylate coating and an electrostatic charge (electrons), in deep and shallow potential wells in the acrylate coating can be caught.

It it was determined that the block formation by adding a second crosslinking and discharge station after the formation of the Acrylate polymer could be eliminated in the first station. The second crosslinking station can be another electron beam lower energy or a plasma treatment station. One Electron beam with an energy of 600 to 1200 eV was used for another Surface hardening and Discharge of the surface of the acrylate polymer. Own at this voltage level most polymer materials have a secondary electron emission coefficient, the higher is 1.0, which therefore results in a surface discharge since for each incident electron emits more than one electron from the surface become. A plasma treatment station achieves the same result, although the mechanism is different. The radiation at one Plasma discharge includes ions and UV radiation. The UV radiation includes very high energy (15 eV) vacuum UV photons, which cause surface crosslinking reinforce while the Ions support the discharge of the film surface.

One alternative method of preventing blocking of the film in the role is the use of monomer formulations, the small ones Levels of additives such as monoacrylate monomers that do not fully crosslink can or partially conductive. This leads to the formation of a "lubricious" and / or antistatic acrylic surface, which inhibits block formation and the formation of a static charge.

B. Transparent ceramic coated barrier films

Environmental constraints result in replacement of certain high-barrier chlorine-containing polymer films by polyester films coated with transparent barrier layers of inorganic materials such as alumina and silicon oxides (SiO _x where x = 1 to 2).

Some food manufacturers have been slow to accept the more costly coated transparent barrier films because of the higher price of the polyester film that appears to be needed to produce transparent coatings with high barrier properties. For this purpose, several experiments were Production of a lower cost transparent barrier made using polypropylene (PP) substrate films. This work showed that the low melting point PP films are generally a poor substrate for deposition of the higher melting point inorganic coatings. Therefore, ceramic-coated transparent barrier films which are currently on the market use a polyester film as a substrate which has higher thermo-mechanical properties than PP.

The present invention relates to the low cost production of high barrier metallized films as well as high barrier PP transparent films utilizing a combination of vacuum polymer coating and surface modification by plasma treatment. A PP film was plasma treated using a 90% N ₂ /10% Ar gas mixture, and a low odor acrylate monomer was deposited and crosslinked with electron beam radiation. The acceleration voltage is typically 10 to 12 keV for an acrylate coating of 1.0 μm. The current (or the number of electrons) varies with the web speed. For a one foot wide web moving at 30.48 to 61 m / min (100 to 200 ft / min), a current of 5 to 10 mA was used.

The transparent films used in the practice of the present invention include alumina, silicas (SiO _x , where x = 1 to 2), tantalum oxide, aluminum nitride, titanium nitride, silicon nitride, silicon oxynitride, zinc oxide, indium oxide, and indium tin oxide. The thickness of the ceramic coating may be in the range of 5 to 100 nm for use as a barrier layer. Preferably, the best barrier properties are obtained in the lower part of the thickness range. The ceramic coating can be deposited by electron beam evaporation.

Two types of transparent barrier films were produced, one using a thin inorganic film of SiO _x , where x = 1 to 2, and Al ₂ O ₃ . The SiO _x film was deposited from a silane gas mixture using plasma deposition, and the Al ₂ O ₃ film was deposited using electron beam evaporation. In this experiment, the task was to see if the thermo-mechanically higher acrylate hybrid film had improved barrier properties, rather than minimizing barrier properties. The results given in Table VIII show that the oxygen and moisture barrier properties of the transparent PP / plasma / acrylate / ceramic film are superior to the control PP / ceramic film.

TABLE VIII OXYGEN (OTR) AND MOISTURE (MVTR) PASSING RATE OF CONTROL PP / CERAMIC AND PP / PLASMA / ACRYLATE / CERAMIC HYBRID FILMS

In packaging applications, it is important that the barrier properties of a film be maintained during the process of processing the film into a pouch. This process exposes the film to stretching and stretching as the film is pulled over a forming sleeve that causes the planar film to conform to a cylindrical opening that faces first at the side, then at the bottom, and at the top after the first automatic insertion of food into the bag is sealed. When a conventional metallized PP film is stretched, the aluminum layer can easily crack, resulting in the loss of the barrier. Since barrier properties as a function of elongation are difficult to measure, aluminum cracking as a function of strain was determined indirectly by measuring the resistance of the aluminum. 5 shows that the deposited on PP aluminum (curve 58 ) far worse mechanical properties than a PP / plasma / aluminum / acrylate / plasma hybrid film (curve 60 ) using 90% N ₂ /10% Ar gas plasma and adhesion promoted deodorized tripropylene glycol diacrylate monomer.

Further study of the structure of aluminum using X-ray diffraction Analysis, transmission electron microscopy and electron diffraction analysis show that the aluminum formed on the control PP surface has large crystals while aluminum deposited in the hybrid film has a much finer crystal structure. Such a crystal structure in combination with excellent aluminum adhesion to the nitrided PP surface and the protective acrylate coating minimizes the formation of microcracks and preserves the original barrier properties of the film. Several packaging tests carried out by a leading manufacturer of snack foods showed these bags made with a monorail of PP / plasma / aluminum / acrylate. The acrylate polymer was prepared by electron beam curing of a tripropylene glycol diacrylate monomer film, which was vacuum dried using the in 1 deposited experimental device produced. The thickness of the acrylate polymer was 1.0 μm. The PP film was first plasma-treated using a gas plasma produced by an Ar / N ₂ gas mixture at a 10% / 90% ratio, and aluminum was applied on top of the plasma-treated surface. The acrylate polymer was applied on top of the thin aluminum metal to prevent needle hole formation due to abrasion of the film surface on rollers in the vacuum chamber and in subsequent processes such as cracking and lamination.

Of the Hybrid film maintained low MVTR and OTR while controlling PP / Al film an increase of about one order of magnitude can show. Table IX shows OTR and MVTR data after film production Printing and after bag production.

TABLE IX. OXYGEN (OTR) AND MOISTURE RATE (MVTR) RATE OF PP / PLASMA / ALUMINUM / ACRYLATE / PLASMA HYBRID FILMS IN DIFFERENT PRODUCTION LEVELS OF SNACK FOOD BAG

III. FILMS FOR PRINTING APPLICATIONS

Benetzungszeitraum von 30 Sekunden

Benetzungszeitraum von 10 SekundenIn the above description of packaging applications, the PP / plasma / metal / acrylate / plasma hybrid film can be printed directly after production without any special preparations. The printing industry uses a broad range of printing inks, which include three main categories: water-based, solvent-based (oil) and 100% solids. Although these inks are formulated for wet different surface types, surfaces are often formulated to be wetted by a particular inking process and apparatus that a food manufacturer has in place. The acrylate hybrid films can be designed to be wetted by various printing ink chemistries. The hydrophobic / hydrophilic and oleophobic / oleophilic surface wetting properties were determined using the solutions shown in Table X. One drop of each of the solutions in Table X was deposited on the surface of an acrylate polymer obtained by electron beam curing the acrylate monomer. If the liquid drop of a particular composition (1-6) does not wet the surface within the specified time period (see footnotes in Table X), the surface is considered to be phobic for that liquid. TABLE X. SOLUTION SCHEME USED FOR FURNISHING TESTS, IN WHICH THE NUMBER '1' IS THE MOST POWERFUL PHIL AND THE NUMBER '6' IS THE MOST STRONG PHOBE

Wetting period of 30 seconds

Wetting period of 10 seconds

Anmerkung: KENSTAT q100 ist eine Handelsbezeichnung von Kenrich Petrochemicals, Inc.About 100 different acrylate formulations were produced and tested for base wetting properties (see list under "Capacitors" above). The results in 6 show that hybrid films with specific surface wetting properties can be formulated to accommodate a broad range of ink chemistry. Some examples of acrylate polymer formulations and their corresponding wetting properties are given in Table XI. TABLE XI. OIL AND WATER RESISTANCE CHARACTERISTICS OF ACRYLATE HYBRID FILMS (PP / Plasma / Acrylate), SEE TABLE X FOR FILLING SCALE NUMBERS

Note: KENSTAT q100 is a trade name of Kenrich Petrochemicals, Inc.

In addition to Printing applications may include surface wetting functionalization PP / acrylate films may be useful in other applications which a surface wetting or a lack thereof is important. For example, a similar to Teflon Surface, the water repels, many large-scale and have commercial applications. An oleophilic surface could be added Film / film capacitor applications are used in which the wound rolls with a dielectric liquid oil-based careful soaked Need to become.

IV. MAGNETIC BANDS

The Need for Storage media of increasingly higher density, the wide use of videotapes a tight format and the development of digital audio and video tape drives to lead to a recording with shorter Wavelength, the one higher Data storage per unit length a volume allows. Such recording tapes use a thin one Metal magnetic coating produced by metal vapor, sputtering and Plating techniques can be obtained. This approach eliminates the polymer binder used in conventional magnetic coatings resulting in ferromagnetic layers with higher saturation magnetization leads, what kind of higher Storage densities favorable is.

If a short wavelength record is used is the Failure or loss of information for a given distance between the recording medium and the magnetic head much higher. Of the Distance loss is represented by the formula 54.6d / w where d is the distance from tape to head and w is the recording wavelength. Therefore, when the surface occurs the magnetic medium or the opposite side are rough, a loss of information when the tape is in front of the head. Out This is why films are made for metallized magnetic tapes used, very expensive, since the surface roughness from both the front and the back accurately controlled have to be to ensure a low degree of roughness. It should be noted that if the roughness of the back too low, the band can then bind and be damaged.

One another problem with thin metal strips is a damage of the magnetic tape due to abrasion resistance and environmental corrosion. Tape manufacturers have developed different ways of dealing with these Restrictions. Radiation curing Materials are becoming common for coating both the front and the back Of the substrate tape used and often become inorganic additives for controlled Roughness and antistatic properties on the backside coating used (US patents 5 068 145, 4 679 340, 4 720 421, 4 781 965, 4 812 351, 4 67 083 and 5,085,911). The existing procedures for the application of radiation-curing Coatings use conventional Application method (roller coating, casting and solution-based) under atmospheric Conditions and for curing UV or electron radiation are used, these in air or in a nitrogen environment.

In the present invention, vapor-phase acrylate coatings are vacuum-deposited, allowing thinner, pin-hole-free and more uniform coatings in line with magnetic coating deposition. Acrylate polymer films deposited on a surface of a polyester film can level surface irregularities by one to two orders of magnitude, depending on the thickness of the acrylate layer. For example, an acrylate coating of 2.0 microns on a surface having rough protrusions of 400 nm reduces the average surface roughness to less than 50 nm. The acrylate polymer was prepared by electron beam curing a hexanediol diacrylate monomer film, which was vacuum dried using the in 1 deposited experimental device produced. The substrate film was first plasma treated using a gas plasma produced by an Ar / N ₂ gas mixture at a 10% / 90% ratio. When a planar film with rough protrusions of 50 nm is used, a hexanediol diacrylate acrylate layer of 1.0 μm or less results in an actually flat film surface having a surface roughness of the order of 1 to 2 nm.

As stated above, a surface with a controlled Roughness on the back of magnetic tape often desired about the friction over Minimize rolling. A hybrid film with a controlled microroughness was produced in the following way. After the deposition of a radiation curing Monomer becomes an electron beam to polymerize the thin monomer film used. For a film thickness of 1.0 μm can be a beam with an acceleration voltage of about 8 to 12 keV are used. When the beam voltage is considerable is decreased, the penetration depth of the electrons becomes proportional reduced. For example, hardens an acceleration voltage of 600 to 1000 eV the surface of Acrylic film, creating a thin Skin is created. The in the exothermic polymerization reaction produced heat and cause the shrinkage of the acrylate film during the polymerization Wrinkling of the skin in a very controlled manner.

A cross section of the folded surface 62a is in 7A shown. The periodicity and depth of wrinkles can be controlled based on the thickness of the monomer film, the accelerating voltage, the current (number of electrons) and the film shrinkage that can be varied by changing the acrylate chemistry. Acrylate materials with a film shrinkage of greater than 5% are beneficial to this process, with shrinkage levels of 15% being preferred. Such monomers include materials such as pentaery trithiacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, tripropylene glycol diacrylate and tetraethylene glycol diacrylate. After production of the folded surface, a second electron beam of higher voltage is used to polymerize the entire monomer film thickness.

The reduced voltage can be achieved by placing a smaller electron beam gun 230 that as a phantom in 1 is shown between the flash evaporation device 28 and the radiation curing agent 30 to be obtained.

In the 7A shown roughened surface 62a Can be used on the back of a magnetic tape to minimize abrasion and facilitate free movement over rollers. Such a surface may also be useful with film / foil capacitors to facilitate the impregnation of capacitor coils with a dielectric fluid.

V. OPTICAL FILTERS

• (A) Der oben beschriebene faltige Film erzeugt bei Metallisierung nach der zweiten Elektronenstrahlhärtung (7B) leuchtende Farbverschiebungsreflexionen, wenn die Faltengröße für eine Interferenz mit dem Umgebungslicht klein genug ist. Obwohl in dieser Arbeit nur ein gleichförmiges Interferenzmuster über die Filmoberfläche produziert wurde, können Farbverschiebungsbilder durch Bemusterung der Faltenfläche 62b und durch Variation der Faltengröße innerhalb eines Bildes produziert werden. Dies kann durch Ersetzen des breiten Elektronenstrahlvorhangs durch einen punktuellen Elektronenstrahl, der zur Bewegung in der X-Y-Achse computergesteuert sein kann und auch durch Modulation der Z-Achse variablen Strom zeigen kann, erreicht werden.
• (B) Ein gleichförmiger Farbverschiebungsfilm 64 wurde unter Verwendung eines relativ ebenen Substratfilms 120 oder eines relativ rauen Films, der mit einer Acrylatbeschichtung eingeebnet wurde, produziert. Die Konfiguration des Farbverschiebungsfilms (in 8 gezeigt) war die folgende: Polyester/Plasma/Metall 1/Acrylat 1/Metall 2/Acrylat 2/Plasma. Das Acrylatpolymer wurde durch Elektronenstrahlhärtung eines Hexandioldiacrylatmonomerfilms, der im Vakuum unter Verwendung der in 1 beschriebenen Versuchsvorrichtung abgelagert wurde, produziert. Der Polyestersubstratfilm wurde zunächst unter Verwendung eines Gasplasmas, das durch ein Ar/N₂-Gasgemisch mit einem 10%/90%-Verhältnis produziert wurde, plasmabehandelt. Das Metall 1 war ein Aluminiumfilm 124, der stark reflektierend ist, mit einer optischen Dichte von 3 bis 4. Das Acrylat 1 war eine dünne Acrylatbeschichtung 122 mit einer Dicke, die 1/4 der Wellenlänge von sichtbarem Licht betrug (0,4 bis 0,7 μm). Das Metall 2 war eine dünne halbtransparente Schicht 124' mit einer optischen Dichte von 0,5 bis 1,5. Das Acrylat 2 ist eine optionale Schutzbeschichtung 122', die eine beliebige Dicke (typischerweise 0,5 bis 3 μm), die adäquate Abriebbeständigkeit ergibt, aufweisen kann. Ein derartiger Hybridfilm führt zu einer gleichförmigen leuchtenden Farbe, die bei Änderung des Betrachtungswinkels zu einer Farbe höherer oder niedrigerer Frequenz verschoben wird.

Polymer films with optical effects, such as color shift, and holographic images are used in a variety of applications, including wrapping films and counterfeit-proof and counterfeit-protective medallions. Two such acrylate hybrid films were produced in a one-step low cost manufacturing process.

• (A) The wrinkled film described above, when metallized after the second electron beam hardening ( 7B ) bright color shift reflections when the wrinkle size is small enough to interfere with ambient light. Although in this work only a uniform interference pattern was produced across the film surface, color shift images can be obtained by patterning the pleat surface 62b and produced by varying the size of wrinkles within an image. This can be accomplished by replacing the wide electron beam curtain with a punctuated electron beam, which can be computer controlled for movement in the XY axis and can also exhibit variable current through Z-axis modulation.
• (B) A uniform color shift film 64 was using a relatively flat substrate film 120 or a relatively rough film that has been leveled with an acrylate coating. The configuration of the color shift film (in 8th shown) was the following: polyester / plasma / metal 1 / acrylate 1 / metal 2 / acrylate 2 / plasma. The acrylate polymer was prepared by electron beam curing of a hexanediol diacrylate monomer film, which was vacuum dried using the in 1 deposited experimental device produced. The polyester substrate film was first plasma-treated using a gas plasma produced by an Ar / N ₂ gas mixture at a 10% / 90% ratio. The metal 1 was an aluminum film 124 which is highly reflective, with an optical density of 3 to 4. The acrylate 1 was a thin acrylate coating 122 with a thickness which was 1/4 of the wavelength of visible light (0.4 to 0.7 μm). The metal 2 was a thin semitransparent layer 124 ' with an optical density of 0.5 to 1.5. The acrylate 2 is an optional protective coating 122 ' which can have any thickness (typically 0.5 to 3 μm) that gives adequate abrasion resistance. Such a hybrid film results in a uniform bright color which shifts to a higher or lower frequency color as the viewing angle changes.

The light beam 66 falls on the color shifting device 64 and a part passes through the semi-transparent metal layer 124 ' and is called a ray 68a through the opaque metal layer 124 reflected. Another part of the incoming light beam 66 is called a ray 68b through the semi-transparent metal layer 124 ' reflected.

Of the The above color shift hybrid film may be for a color shift on be made on both sides. That said, it could also be a color shift through the transparent polyester substrate film when the Color shift stack is symmetrical. Such a structure that would be following: polyester / semi-transparent aluminum / ¼ λ acrylate / reflective aluminum / ¼ λ acrylate / semitransparent Aluminum. When considering the hybrid film model given above, it is also relatively easy for a person skilled in the art to a color shift pigment by releasing the color shift stack to produce from the polyester substrate. This can be done by coating of the polyester substrate with a polystyrene layer. The color shift stack is then deposited on the polystyrene, which are dissolved in a solvent can, whereby symmetrical color shift flakes are formed, which are reduced to a finer color shift pigment can.

VI. FLEXIBLE CABLE

at electrical cables, such as those used in aircraft for distribution of energy used to different parts of the aircraft can an arc formation take place, which produces a so-called "electrical trajectory", the fire outbreaks to lead can. The use of these films in military aircraft was through the US Navy and later the US Army and Air Force due to poor electrical resistance Railway formation leading to several documented cases of fire outbreaks and even the loss of a military one Aircraft, forbidden. A solution was the replacement of the thermally and mechanically robust polyimide films, have the poor web forming properties by len with polytetrafluoroethylene len ("Teflon") coated Wire that has outstanding arc trajectory properties. however the Teflon coating is quite soft and can be easily damaged. A solution This problem is the placement of Teflon on a polyimide film (see entry Chemfab in the following Table XII). This Hybrid film has teflon-like Trajectory properties with outstanding thermal and mechanical Properties.

In the present invention, the reduction of electrical traction is achieved through the use of a hybrid film utilizing a combination of a Teflon-like vacuum polymer coating and surface modification by a plasma treatment. An electric arc trajectory test was developed to simulate the properties of a cable insulation. A high voltage, high impedance (5 to 15 kV) AC voltage was placed between two flat metal plates that were 12.7 cm (5 inches) long, 5 cm (2 inches) wide, and 1 / 40.6 cm (16 inches) thick , created. The test specimens (in the form of 2.5 x 10 ^-5 to 1.5 x 10 ^-4 m (1 to 6 mil) thick films) were wrapped around the plates and the two plates were fixed against each other along their length on a plane , The distance between the plates was adjusted to about 1 mm and the tension was increased until an arc at one of the two opposite sets of corners in the two plates intentionally exposed (not covered with the test films) to prevent the formation of the Arc was created. The polymer films begin to burn as soon as the arc forms. The rate of arc movement (burning of the film) accurately reflects the ability of the sheet material to form. The system was tested using known materials, such as Teflon and Kapton films, which have low or high arc path forming rates.

Table XII. Arc lamination resistance of several polymer films

A functionally similar hybrid film was produced by depositing a fluorine-containing acrylate film on one or both sides of Kapton (DuPont Film) and PBO (Dow Chemical Film). Table XII shows a clear relationship between the thickness of a fluoroacrylate coating on PBO and Kapton films of 25 μm. The fluoroacrylate coating consisted of a 25%: 75% mixture of hexanediol diacrylate lat. (HDODA): perfluoroalkylsulfonamide and was then irradiated with an electron beam using the techniques described in U.S. Pat 1 networked device described. For the PBO coated films, the improvement in arc path formation was parallel to the coating thickness until a critical thickness of 12 μm was achieved. Beyond this point, the formation resistance was equal to that of PTFE. At a coating thickness of 23 μm, it was not possible to strike a sustainable arc, and therefore an apparent arc-tracing resistance better than that of PTFE was obtained. Table XIII shows the filming resistance of the 12 μm coated PBO and Kapton films along with several other commercial films tested under the same conditions and incorporated as benchmarks to obtain a comparison means for the arc path forming properties of the fluoroacrylate coatings.

TABLE XIII. ARC FILMING DISTANCE OF FLOOR ACRYLATE COATED PBO AND KAPTON FILMS

COMMERCIAL USE

It it is believed that the hybrid polymer films comprising a polymer film, a plasma-treated surface, a vacuum-deposited radiation-curable acrylate polymer having a plasma-treated surface include a variety of uses in food packaging films, dünnschichtmetallisierten and foil capacitors, flexible electric cables, metallised Magnetic tapes, optical variable films and other applications, the films such as PP and PET use, find.

Even though certain embodiments here are disclosed in the present invention, without the expert Further, it is clear that various changes and modifications of an obvious nature, and all such changes and modifications are considered to be within the scope of the invention the attached claims is defined as falling.

Claims (19)

Hybrid polymer film ( 20 ' ), wherein the hybrid polymer film ( 20 ' ) comprises: (a) a first polymer film ( 120 ), (b) a plasma-treated surface of the polymer film ( 120 (c) a radiation-polymerized monomer film formed by vacuum deposition ( 122 ) deposited on the plasma-treated surface, and (d) a plasma-treated surface on the radiation polymerized monomer film (Fig. 122 ). Hybrid polymer film ( 20 ' ) according to claim 1, wherein the first polymer film ( 120 ) is either a thermoplastic polymer or a thermosetting polymer. Hybrid polymer film ( 20 ' ) according to claim 1, wherein the plasma treatment is selected using an inert gas selected from the group consisting of N ₂ , Ar, Ne, or a reactive gas selected from the group consisting of O ₂ , CO ₂ , CF ₄ , or a mixture thereof as a plasma gas. Hybrid polymer film ( 20 ' ) according to claim 1, wherein the radiation-polymerized monomer film ( 122 ) is an acrylate monomer. Hybrid polymer film ( 20 ' ) according to claim 1, further comprising an inorganic layer ( 124 ) on at least part of at least one side of the radiation-polymerized monomer film ( 122 ). Hybrid polymer film ( 20 ' ) according to claim 5, wherein the inorganic layer ( 124 ) from the group of aluminum, zinc, nickel, cobalt, iron, nickel on aluminum, iron on aluminum, zinc on silver, zinc on copper, zinc on aluminum, a nickel-cobalt alloy, a nickel-cobalt-iron alloy , Alumina, a silica, tantalum oxide, aluminum nitride, titanium nitride, silicon nitride, silicon oxynitride, zinc oxide, indium oxide and indium tin oxide. Hybrid polymer film ( 20 ' ), wherein the hybrid polymer film ( 20 ' ) comprises: (a) the first polymer film ( 120 ), (b) the plasma-treated surface of the polymer film ( 120 ), (c) a first inorganic layer ( 124 ) on the plasma-treated surface, (d) the radiation-polymerized monomer film formed by vacuum deposition ( 122 ) deposited on the inorganic layer ( 124 ) and (e) the plasma-treated surface on the radiation-polymerized monomer film ( 122 ). Hybrid polymer film ( 20 ' ) according to claim 7, further comprising a second inorganic layer ( 124 ' ) on at least a portion of the radiation-polymerized monomer film ( 122 ). Hybrid polymer film ( 20 ' ) according to claim 8, further comprising a second radiation-polymerized monomer film formed by vacuum deposition ( 122 ) on at least a part of the second inorganic layer ( 124 ' ). Hybrid polymer film ( 20 ' ) according to claim 9, wherein the first inorganic layer ( 124 ) is an opaque metal layer having an optical density of greater than 3.0 and wherein the second inorganic layer ( 124 ' ) is a semi-transparent metal layer having an optical density of 0.5 to 1.5. Hybrid polymer film ( 20 ' ) according to claim 10, wherein the radiation-polymerized monomer film ( 122 ) has a thickness in the range of 0.5 to 3 microns, which has been chosen so that interference with radiation having a wavelength in the range of 0.4 mm to 15.0 mm and on the second inorganic layer ( 124 ' ) is received. Hybrid polymer film ( 20 ' ) according to claim 1, wherein the hybrid polymer film ( 20 ' ) comprises: (a) the first polymer film ( 120 ), (b) a plasma-treated surface of the polymer film ( 120 ), (c) a first inorganic layer ( 124 ) on the first polymer film ( 120 ), (d) a second inorganic layer ( 124 ' ) on the first inorganic layer ( 124 ), (e) a radiation-polymerized monomer film formed by vacuum deposition ( 122 ) deposited on the second inorganic layer ( 124 ' ), (f) a third inorganic layer ( 124 ) on the radiation polymerized film ( 122 ), and (g) a fourth inorganic layer ( 124 ) on the third inorganic layer ( 124 ). Hybrid polymer film ( 20 ' ) according to claim 12, wherein the first polymer film ( 120 ) is coated with a polymer layer which is soluble in organic solvents. Hybrid polymer film ( 20 ' ) according to claim 1, wherein the hybrid polymer film ( 20 ' ) comprises: (a) the first polymer film ( 120 ), (b) a plasma-treated surface of the polymer film ( 120 ), (c) a first inorganic layer ( 124 ) on the first polymer film ( 120 (d) a first radiation-polymerized monomer film formed by vacuum deposition ( 122 ), which on the first inorganic layer ( 124 ), (e) a second inorganic layer ( 124 ' ) on the first radiation-polymerized monomer film ( 122 (f) a second radiation-polymerized monomer film formed by vacuum deposition (FIG. 122 ' ) deposited on the second inorganic layer ( 124 ' (g) a plasma-treated surface on the second radiation-polymerized monomer film ( 122 ' ). Hybrid polymer film ( 20 ' ) according to claim 1, wherein the radiation-polymerized monomer film formed by vacuum deposition ( 122 ) has a controlled microroughness. Hybrid polymer film ( 20 ' ) according to claim 15, wherein the controlled microroughness of the deposited radiation-polymerized monomer film ( 122 ) by controlled periodicity and depth of wrinkles in the polymerized film ( 122 ) provided. Hybrid polymer film ( 20 ' ) according to claim 15 or claim 16, wherein the radiation-polymerized monomer film formed by vacuum deposition ( 122 ) is an acrylate monomer. Hybrid polymer film ( 20 ' ) according to any one of claims 15 to 17, wherein the controlled microroughness of the deposited radiation-polymerized monomer film ( 122 ) by curing the surface of the monomer films ( 122 ) such that a thin skin having a wrinkled surface is produced and subsequent polymerization of the total thickness of the monomer film ( 122 ). Hybrid polymer film ( 20 ' ) according to any one of claims 15 to 18, further comprising an inorganic layer ( 124 ) on at least part of one side of the radiation polymerized monomer film ( 122 ).